Argyrodites doped with thiophilic metals

Abstract

Provided herein are solid materials that are ionically conductive and electrochemically stable. Embodiments of the solid materials are argyrodite-type compositions that have high ionic conductivity. The compositions include small amounts of thiophilic metals, whose binary sulfides do not react with water to hydrogen sulfide (H 2 S). As such, H 2 S release is minimized or eliminated. Also provided are methods of fabricating the materials and batteries and battery components containing the materials.

1 . A composition comprising:
 an alkali metal argyrodite sulfide-based ion conductor doped with a thiophilic metal,   wherein the thiophilic metal is selected from manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), mercury (Hg), molybdenum (Mo), or a combination thereof, wherein a ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is no more than 1:20.   
     
     
         2 . The composition of  claim 1 , wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is at least 1:120 and no more than 1:20. 
     
     
         3 . The composition of  claim 1 , wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is at least 1:50 and no more than 1:20. 
     
     
         4 . (canceled) 
     
     
         5 . (canceled) 
     
     
         6 . The composition of  claim 1 , wherein the alkali metal is lithium (Li), sodium (Na) or potassium (K). 
     
     
         7 . The composition of  claim 1 , wherein the alkali metal is lithium. 
     
     
         8 . A composition comprising:
 an alkali metal argyrodite sulfide-based ion conductor doped with a thiophilic metal, wherein the thiophilic metal is selected from manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), mercury (Hg), molybdenum (Mo), or a combination thereof, wherein a ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is no more than 1:20 and wherein the alkali metal argyrodite sulfide-based ion conductor is given by the formula:
     A   7−x−(z*y)   M   z   y   PS   6−x   Hal   x    
   wherein   A is the alkali metal;   M is the thiophilic metal;   Hal is selected from chlorine (Cl), bromine (Br), or iodine (I);   z is the oxidation state of the thiophilic metal;   0<x≤2; and   0<y<(7−x)/z.   
     
     
         9 . The composition of  claim 8 , wherein z>+1. 
     
     
         10 . The composition of  claim 8 , wherein z=+2. 
     
     
         11 . The composition of  claim 8 , wherein 1≤x≤1.6. 
     
     
         12 . The composition of  claim 8 , wherein 0.≤y≤2−x. 
     
     
         13 . The composition of  claim 8 , wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is at least 1:120 and no more than 1:20. 
     
     
         14 . The composition of  claim 8 , wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is at least 1:50 and no more than 1:20. 
     
     
         15 . A composition comprising:
 an alkali metal argyrodite sulfide-based ion conductor doped with a thiophilic metal, wherein the thiophilic metal is selected from manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), mercury (Hg), molybdenum (Mo), or a combination thereof, wherein a ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is no more than 1:20 and wherein the alkali metal argyrodite sulfide-based ion conductor is given by the formula: A 7−x+n−(z*y) M z   y PS 6−x Hal x+n      wherein   A is the alkali metal;   M is the thiophilic metal;   Hal is selected from chlorine (Cl), bromine (Br), or iodine (I);   z is the oxidation state of the thiophilic metal;   0.05≤n≤0.9   −3.0x+1.8≤n≤−3.0x+5.7   0≤y<(7−x)/z; and   0<x≤2.   
     
     
         16 . The composition of  claim 15 , wherein z>+1. 
     
     
         17 . The composition of  claim 15 , wherein z=+2. 
     
     
         18 . The composition of  claim 15 , wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is at least 1:120 and no more than 1:20. 
     
     
         19 . The composition of  claim 15 , wherein the ratio of thiophilic metal atoms to sulfur atoms in the alkali metal argyrodite sulfide-based ion conductor is at least 1:50 and no more than 1:20. 
     
     
         20 . The composition of  claim 1 , wherein the alkali metal argyrodite sulfide-based ion conductor is single phase material. 
     
     
         21 . A composition comprising:
 a composite film of particles comprising an argyrodite according to  claim 1  in a polymer.   
     
     
         22 . (canceled) 
     
     
         23 . The composition of  claim 21 , wherein the polymer is not ionically conductive. 
     
     
         24 .- 26 . (canceled) 
     
     
         25 . The composition of  claim 21 , wherein the film is between 0.5 wt %-60 wt % polymer. 
     
     
         26 . The composition of  claim 21 , wherein the film is between 5 wt %-30 wt % polymer. 
     
     
         27 . A composition comprising:
 an electrochemically active material, an alkali metal argyrodite sulfide-based ion conductor according to  claim 1 , carbon electrically conductive particles, and an organic polymer.   
     
     
         28 .- 33 . (canceled)